Heavy-duty industrial grease



Patented Nov. 15, 1949 2,488,293 HEAVY-DUTY INDUSTRIAL GREASE Arnold J. Holberg, El Dorado,

Lion Oil Company, El Dorado,

tion of Delaware Ark., assiznor to Aria, a corpora- No Drawing. Application April 12, 1946, Serial No. 661,892

12 Claims.

This invention relates to new asphaltic compounds and to the method of making the same, and more particularly to the production of semisolid materials suitable for use as lubricants on heavy bearing surfaces and gears which operate at comparatively slow speed and as a coating on surfaces to be protected from atmospheric and other corrosion agencies. The compounds are of particular utility for application on cables and movingparts of hydraulic machinery, and on metal parts exposed to the out-of-doors because of the high adhesiveness they have to metals under adverse conditions of moisture and dust, and because of their resistance to flow at elevated atmospheric temperatures. The high flash point and extreme stability to heat which certain of these products possess are highly desirable properties in lubrication of heavy industrial machinery such as rolling mills.

According to my invention the compounds are prepared by a two-step process. A residuum carefully reduced without decomposition from a crude oil to have a flash point, 0.0. C., (ASTM D92-45) of at least 400 F., but preferably 475 F. or higher, is air blown at a temperature in the range of 400 F. to 550 F. in the presence of a minor amount of a catalyst or agent which promotes an increase in penetration of the product for a given softening point. The blowing is continued until the softening point (R and B), (ASTM D36-26) becomes at least 230 F. and not more than 350 F. The type of catalyst or agent and amount to employ are selected according to its action on the particularresiduum to obtain a product with a needle penetration at 77 F., (ASTM D5-25), for a given softening point such that the penetration temperature susceptibility (PTS) calculated according to the relation given hereinafter will be within the range of 0.005 to 0.015.

log 800log penetration at 77 F softening point (R and B) F.-77

As the second step, this air-blown asphalt is blended (fluxed back) to obtain a compound with the desired dropping point (ASTM D566-142) by addition of from 15 to '70 percent of a residuum of the type air-blown or with other residua or with a lubricating oil distillate or fraction or with a gas oil fraction, or mixtures thereof. The exact amount and choice of blending stock depends upon the characteristics desired, as will be explained hereinafter. For most purposes the dropping point is required to be above F. and the unworked penetration at 77 F. as determined with the grease cone, g., 5 sec., (ASTM D217- 44T) in the range of '75 to 350 mm./10, but for certain applications as for greases to be used at low temperatures, products of higher penetration and lower dropping point may be desired.

It is known that products of a fairly high penetration for a given softening point can be obtained by air-oxidation of low viscosity and low flash point paraflinic residua or lube stocks. But from a given base no control is had over the body or plasticity of the product. Such asphalts are not suitable for many applications because they flow at high atmospheric temperatures and tend to be unstable and exude oils and to break down under working. In general, they are not suited for heavy duty service. Because of their high parafilnicity they show adhesion to metal surfaces and can be displaced relatively easily by water. Their weathering characteristics are poor and they cannot be recommended as protective coatings for outdoor applications.

With the aid of catalysts asphaltic products which are high in penetration for a given softening point can be air blown from most types of crude oil residua. These products, when blown from naphthenic or asphaltic residua have been found to be stable in nature. Products which are high in flash point can be obtained by proper selection of the base and catalyst. However, this direct process also does not offer control of the body and plasticity of the products. From a given base a product will be obtained which because '4 and in general are less stable to heat and weathering influences. Preparation from an asphaltic or naphthenic type base results in a table product with a relatively high combined sulphur content. These sulphur compounds, of its body and other properties may or may not which ar polar in nature, increase the adhesivebe suitable for a particular application. ness' of the compound to metals and are known The process which is the subject of this invento raise the film strength of lubricating greases. tion has been found to be highly flexible and to Another feature is that the air blowing of aspermit a multitude of products of different charphaltic or naphthenic compounds proceeds along acteristics to be prepared from a given base sima somewhat diiferent path than does the air blowply by variation of the blending stock. Fluxing ing of a parafflnic type of oil. With the latter a with residua of the air blown type to obtain the considerable increase in saponification number base will produce a product which is more ductile is noted, part of which is due to the formation of and adhesive than a product blown directly with potentially corrosive hydroxy acids. The time the aid of catalyst to the same dropping point required to obtain a, given softening point is relaand penetration. With addition of a lube stock tively long. A considerable content of free carto the blown base a higher penetration will be obbon may be formed unless the temperature is tained for the same dropping point and a large held below 450 F. Asphaltic or naphthenic change will be found in body, with this product types of residuum upon air-blowing increase in relatively short and low in ductility and more oily softening point in a relatively short time and only andless adhesive. With employment of paraflinic minor amounts of saponifiable compounds are lube stocks for fluxing extreme shortness can be formed. The action of the catalysts or agents obtained; in fact, the product can become granuin this process is apparently to cause a formalar in appearance without showing a tendency to tion of fractions which, without causing a loss separate into layers. With a given base and in homogeneity in the asphalt, impart a very low choice of the fluxing stock, besides control of the penetration susceptibllit plasticity and consistency. and adhesiveness, the In preparation of products, except those for weathering properties can be markedly influuse at low temperatures, bases and fluxing stocks enced. Also, the product obtained has a lower 30 normally are selected which show a flash point, ash content than if the base were directly blown C. O. C., of at least 400 but preferably 475 F. with an inorganic catalyst to a given dropping or higher. The products then obtained are repoint and consistency since less catalyst per unit sistant to hardening by evaporation losses and of final product is required by the fluxing process have been found to be very stable in service, disclosed herein. Thus there is, besides the adwhereas products of lower flash point harden vantage of lower ash content, a matter of econoafter a short period of use. my. Illustrations of the type of agents which can Variation of the dropping point and consistency be used are the phosphorus catalysts which are relationship of the grease also can be obtained the subject of my Patent No. 2,450,756. Other by control of the softening point and PTS of the catalysts are the metallic salts disclosed by Abson air-blown asphalt. Thus, a base with a high in Patent No. 1,782,186, and the metallic halide softenin point and low PTS will flux back to metal powder combinations of my Patent No. a product of softer consistency for a given drop- 2,421,421. Considerable variations are found in ping point. Contrariwise a product of low softenthe action of these catalysts on residua deing point and high PTS will produce a more solid pendent upon the particular crude from which grease for a given dropping point. they were derived. But the essential feature is A paraflinic type of base is not normally emthat the air-blowing should be conducted to have played since the desired consistency for a given the softening point and the PTS of the blown dropping point can be obtained by fluxing bases base within the ranges as given heretofore. air-blown from naphthenic or asphaltic residua For purposes of illustration the method of in the presence of a catalyst. Products from a preparation and properties of several compounds paraflinic base tend to break down upon working are shown in Table I.

TABLE 1 Preparation and properties of asphaltic compounds Properties of Base Blending Stock Catalyst and per Base air blown from cent by weight S. P. (R genial: (11;; and B) F. (Needle), PTS Type by -I weight Smackover residuum of 25 sec. float Zn G1, 2.0 and 279 135 0. 0069 Base Flux 35 at F. and 480 F. flash Cu powder, 0. O. C. 0.5. As 1 P 0, 3.0 801 12-3 0. 0065 Heavy Naphthenic lube stock of 30 207 sec. S. Univ. Vis. at 210 F. A51 P 0 l.8 296 93 0.0077 SAE 40 Parailinic base lube oil". 40 As 1 P 0 296 93 0. 0077 Smackover Virgin Gas Oil 30 Sehuler residuum of 20 sec. float at P 0, 3.0 248 176 0. 0069 Base Flux 25 122 F.and450F.flash,C.O.C. Schuler residuum 01'32 sec. float at FeCP, 3.0 3% 66 0. 0078 SAE 30 Paraflinic base oil 25 122F.and490F.fiash 0.0.0. Ken- Lynn residuum of 27 sec. float F00], 3.0 325 59 0. 0082 Base Flux 35 :3 132 F. and 500 F. Flash, 0. As 7 P 0, 2.0 283 40 0. 0114 SAE 30 Parafiinlc Base lube oil".

TABLE I Properties of Compound Exam .le Catalyst and per No. Base alr'blown from cent by weight ,2 1? 2 3:!" Flash Point Remarks Point, (Cone), at 125 "F. rum/l F., cm

l Smackoverrcsidunmol25sec.float ZnCl, 2.0 and 178 100 0.3 480 Highly homogeneous, bright surat 122 F. and 480 F. flash Cu powder, face. Ductile and highly ad- O. 0. C. 0.5. hcsive.

2 Asl P 0, 3.0 230 154 0.0 500 Highly homogeneous, bright surface. Ductile but somewhat shorter in body than 1.

3 As 1 P 0, 1.8 220 158 0.0 490 Surface somewhat dull. No tendency to separate. Medium short v in body.

4 Asl P O".l. 130 239 2 230 Very fluid and workable grease at low temperature. Highly lrrordnogcneous. Medium short in 5 Schuler residuum of sec. float P O ,3.0. 185 162 0.2 460 Surface slightly dull. No tendency at 132 F. and 450 F. flash, C. 10 dscparutc. Medium short in 0. l. o y.

(l Schiller residuum of 32 see. float FcCl- 3.0 180 170 0.2 480 Slight granular appearance, very at 122 F. and 490 F. flash C. (lull 'surface. No tendency to 0. 0. separate. Very short body.

7 Kerr Lynnresiduumof27sec.l'loat FeCl, 3.0 191 132 0.2 500 Slight granular appearance, very at 122 F. and 500 F. Flash, dull surface. No tendency to C. 0. 0. separate. Short body.

8 As? P 0", 2.0 175 200 0.0 485 Smooth appearance, dull surface. N o tendency to separate. Very short body.

1 For method of test see footnote. Table II.

Residua from three types of Arkansas crude oils which vary widely in characteristics were blown in the presence of catalysts to form bases. The well known Smackover crude oil is asphalticin nature. Schuler crude oil is of the paraifinicnaphthenic type and distills to a residue somewhat more naphthenic than most crude oils from the mid-continent area. Kerr Lynn crude oil is highly paraffinic in nature and contains a low content of asphalt. Example N... 1 describes a product prepared from a Smackover residuum of seconds float at 122 F. (ASTM D139-2'7'). This residuum was air-blown in the presence of a zinc chloride-copper powder catalyst at a temperature of 480 F. to a softening point (R and B) of 279 F. and a needle penetration at 77 F. of 135. The PTS of this blown asphalt calculated to be 0.0069. To this blown base 35% by weight of the Smackover residuum was added to obtain a product of 178 F. dropping point and with a cone penetration of 160 mm./10 and a flash noint, C. O. C., of 480 F. The flow shown at 125 F. after two hours time was 0.3 cm. The product was homogeneous with a bright black surface and was of relatively high ductility and adhesiveness. This compound is well suited as a heavy duty grease on outside gears and cables. Besides action as a lubricant, lasting protection from corrosion will also be ofiered because of the ability of these compounds to displace water from metal surfaces and to resist weathering action.

The product of Example No. 2 was obtained by the addition of of a naphthenic lube stock derived from Smackover crude oil to a base airblown from the Smackover residuum of No. 1, but in the presence of phosphorus anhydride as the catalyst. A compound of higher dropping point, but with about the same penetration, was obtained. This product differed from that of Example No. 1 in that it was somewhat shorter in body and showed no flow at 125 F. Application of this product can be made as a protective coating for pipe and metal structures, and as a grease under high atmospheric temperature conditions. Example No. 3 shows the product obmonths showed no separation of oil. This prod-v uct, because of its shortness, would be better suited for pressure gun application. Example No. 4 describes the preparation and properties of a grease which is suitable for low temperature application. In this case the base of Example No. 3 was fluxed with 30% of a gas oil distilled from Smackover crude. The flash point was low, which 0 would make it unsuitable for operation at temperatures much above F. At 32 F. the product was still readily workable.

The products of Examples 5 and 6 were prepared by fiuxing bases blown from Schuler residuals. The Schuler base, because of its higher content of parafiinic hydrocarbons, fluxed to compounds which were shorter in body. The appearance was somewhat granular, which indicated lack of homogeneity; however, no tendency to separate on storage or when heated at F. for five hours could be noted. These products would be desirable as greases where a short body was required. The grease of Example 6 would be especially desirable for application if a small resistance to drag would be of importance, because of its very short body.

The products described by Examples '7 and 8 were prepared by fiuxing the air-blown residual of Kerr Lynn crude oil. Products which were stable to both heat and storage were obtained in both cases, even though the disturbed surfaces were dull and the products somewhat granular in appearance. Upon working considerable loss in structure and decrease in flow resistance was noted. The shortness of body would be an adamazes 7 vantage in certain applications. These products would not have suflicient weather resistance to be recommended for application as outdoor protective coatings.

As an example of the preparation of a product suitable for application as a protective coating or as a heavy duty grease on a commercial scale, the following example is cited:

One hundred barrels of asphaltic residuum steam and vacuum reduced from Smackover crude oil and showing a float time at 122 F. of 23 seconds and a flash point, C. O. C., of 475 F. was charged to a blowing still. Six hundred pounds of phosphorus pentoxide were added to the flux charge and the mixture air-blown at a temperature of around 460 F. An asphalt with plasticlike properties and a softening point of 296 F., (R and B) and a needle penetration at 77 F. of 93 was obtained after 15 hours of air-blowing. The PTS of this product calculated to be 0.0072.

This plastic asphalt was fluxed with Smackover residuum of 23 seconds float time at 122 F. and 475 F. flash point. The addition of 21 percent of the flux by weight produced a compound with properties as shown under Example No. 1 of Table II. A portion of this product was barreled for use as a grease and as a protective coating for outdoor applications. To the remainder, additional flux was added to have a content of 37 percent to obtain the product of Example No. 2, a heavy duty gear lubricant.

TABLE II Properties of heavy duty greases Flow test procedure: .A portion of the sample was poured to a uniform depth of 0.32 cm. into 11 suitable amalgamated mold 4 cm. wide by 6 cm. long, placed on a bri ht tin panel. After cooling at room temperature for two hours. the mold was removed and the panel containing he sample placed in an oven maintained at 125 F. During the test the panel was mounted at an angle of 75 degrees with the horizontal. After two hours had elapsed the total movement in cms. of the specimen was reported as the flow.

The grease of Example No. 2 was found easy of application and still possessed a dropping point of 185 F. and was resistant to flow under normal atmospheric temperatures.

The invention has been described in detail for the purpose of illustration, but numerous modifications and variations may be resorted to without departing from the spirit of the invention.

I claim:

1. A lubricating grease consisting essentially of a blend of an air-blown asphaltic product with from 15 to 70 percent of a petroleum fraction having at least the boiling point of gas oil, said asphaltic product being air-blown from a base petroleum residuum of greater than 375 F. flash point in the presence of a small quantity of a catalytic agent which acts to lower the penetration-temperature susceptibility, the air-blown base having a softening point within the range of 230 to 350 F. and a PTS within the range of 0.005 to 0.015.

2. A lubricating grease consisting essentially of a blend of an air-blown asphalt product with from 15 to 70 percent of a petroleum fraction having at least the boiling point of gas oil, said asphaltic product being air-blown from a base petroleum residuum of greater than 375 F. flash point in the presence of a small quantity of a catalytic agent which acts to lower the penetration-temperature susceptibility, said agent comprising a phosphorus containing catalyst, the airblown base having a softening point within the range or 230" to 350 F.- and a PTS within the range of 0.005 to 0.015.

3. A lubricating grease consisting essentially of a blend of an air-blown asphaltic product with from 15 to 70 percent of a petroleum traction having at least the boiling point or gas oil, said asphaltic product being air-blown from a base petroleum residuum or greater than 375 F. flash point in the presence of a small quantity of a catalytic agent which acts to lower the penetration-temperature susceptibility, said agent comprising a metal salt, the air-blown base having a softening point within the range of 230 to 350 F. and a PTS within the range of 0.005 to 0.015.

4. A lubricating grease consisting essentially of a blend of an air-blown asphaltic product with from 15 to 70 percent of a petroleum fraction having at least the boiling point of gas oil, said asphaltic product being air-blown from a base petroleum residuum of greater than 375 F. flash point in the presence of a small quantity of a catalytic agent which acts to lower the penetration-temperature susceptibility, said agent comprising a. metal halide-powdered metal combination, the air-blown base having a. softening point within the range of 230 to 350 F. and 9. PTS within the range of 0.005 to 0.015.

5. A lubricating grease consisting essentially of a blend of an air-blown asphaltic product with from 15 to 70 percent of a petroleum fraction having at least the boiling point of gas oil, said asphaltic product being air-blown from a base petroleum residuum of greater than 375 1". flash point in the presence of a small quantity of a catalytic agent which acts to lower the penetration-temperature susceptibility, said base petroleum residuum being a non-paraflinic residuum, the air-blown base having a softening point within the range of 230 to 350 F. and 9. PTS within the range of 0.005 to 0.015.

6. A lubricating grease consisting essentially of a blend of an air-blown asphaltic product with from 15 to 70 percent of a petroleum fraction having at least the boiling point of gas oil, said asphaltic product being air-blown from a base petroleum residuum of at least 400 F. flash point in the presence of a small quantity of a catalytic agent which acts to lower the penetration-temperature susceptibility, the air-blown base having a softening point within the range of 230 F. to 350 F. and a PTS within the range of 0.005 to 0.015.

7. A lubricating grease consisting essentially of a blend of an air-blown asphalt product with from 15 to 70 percent of a petroleum fraction having at least the boiling point of gas oil, said asphaltic product being air-blown from a base petroleum residuum of at least 475 F. flash point in the presence of a small quantity of a catalytic agent which acts to lower the penetration-temperature susceptibility, the air-blown base having a softening point within the range of 230 to 350 F. and a PTS from 0.005 to 0.010.

8. A lubricating grease consisting essentially of a blend of an air-blown asphaltic product with from 15 to 70 percent of a petroleum fraction having at least the boiling point of gas oil, said asphaltic product being air-blown from a base petroleum residuum of greater than 375 F. flash point in the presence of a small quantity of a catalytic agent which acts to lower the penetration-temperature susceptibility, the air-blown base having a softening point within the range of 230 to 350 F. and a PTS from 0.005 to 0.010.

9. A lubricating grease consisting essentially of a blend of an air-blown asphaltic product with from to '70 percent of a petroleum fraction having at least the boiling point of gas oil, said asphaltic product being air-blown from a base petroleum residuum of greater than 375 F. flash point in the presence of a small quantity of a catalytic agent which acts to lower the penetrationtemperature susceptibility, the air-blown base having a softening point within the range of 230 to 350 F. and a PTS within the range of 0.005 to 0.015, the blended lubricating grease having a dropping point above 130 F.

10. A lubricating grease consisting essentially of a blend of an air-blown asphaltic product with from 15 to '70 percent of a petroleum fraction having at least the boiling point of gas oil, said asphaltic product being air-blown from a naphthenic base petroleum residuum of greater than 375 F. flash point in the presence of a small quantity of a catalytic agent which acts to lower the penetration-temperature susceptibility, the air-blown base having a softening point within the range of 230 to 350 F. and a PTS within the range of 0.005 to 0.015.

11. A lubricating grease consisting essentially of a blend of an air-blown asphaltic product with from 15 to 70 percent of a petroleum fraction having at least the boiling point of gas oil, said asphaltic product being air-blown from an asphaltic base petroleum residuum of greater than 375 F. fiash point in the presence of a small quantity of a catalytic agent which acts to lower the penetratlon-temperature susceptibility, the air-blown base having a softening point within the range of 230 to 350 F. and a PTS within the range of 0.005 to 0.015.

12. A lubricating grease consisting essentially of a blend of an air-blown asphaltic product with from 15 to percent of a petroleum fraction having at least the boiling point of gas oil, said asphaltic product being air-blown from a semiasphaltlc base petroleum residuum of greater than 375" F. flash point in the presence of a small quantity of a catalytic agent which acts to lower the penetration-temperature susceptibility, the air-blown base having a softening point within the range of 230 to 350 F. and a PTS within the range of 0.005 to 0.015.

ARNOLD J. HOIBERG.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Pub. Corp. (1937), New York, pages 39 and 766.

. Certificate of Correction Patent No. 2,488,293 November 15, 1949 ARNOLD J. HOIBERG It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 2, line 31, after the word show insert low; column 4, line 4, for table read stable;

and that the said Letters Patent should be read with these corrections therein that the se ne may conform to the record of the case in the Patent Oflice.

Signed and sealed this 4th day of April, A. D. 1950.

THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

